CN110330050A - A kind of Li-La-Ti oxygen material and preparation method thereof, H2S gas sensor - Google Patents
A kind of Li-La-Ti oxygen material and preparation method thereof, H2S gas sensor Download PDFInfo
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- CN110330050A CN110330050A CN201910228800.1A CN201910228800A CN110330050A CN 110330050 A CN110330050 A CN 110330050A CN 201910228800 A CN201910228800 A CN 201910228800A CN 110330050 A CN110330050 A CN 110330050A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The present invention relates to a kind of Li-La-Ti oxygen materials and preparation method thereof, H2S gas sensor, belongs to H2S gas sensitive technical field.Preparation method of the invention, comprising: 1) provide lithium source, lanthanum source, complexing agent, titanium source, ethylene glycol, polyethylene glycol oxide and 1,2- propylene oxide is dissolved in the solvent heat precursor liquid of solvent formation；2) solvent heat precursor liquid is warming up to 100~300 DEG C of 3~168h of reaction, separation of solid and liquid obtains Li-La-Ti oxygen presoma powder；3) by Li-La-Ti oxygen presoma powder be sintered to get.Preparation method of the invention, complexing agent and ethylene glycol can make the energy minimization of system, and during subsequent solvent heat, chelate can tend to the spherical forming core of minimum energy, improve the specific surface area of Li-La-Ti oxygen；Polyethylene glycol oxide and 1,2- propylene oxide can effectively improve interface state, improve the stability of system, and leave porous structure after sintering, further increase the specific surface area of Li-La-Ti oxygen.
Description
Technical field
The present invention relates to a kind of Li-La-Ti oxygen materials and preparation method thereof, H2S gas sensor, belongs to H2S gas sensitive skill
Art field.
Background technique
H2S is a kind of great toxic gas of harmfulness, has the stink for being similar to the egg that rots.Its mucous membrane to human body
With strong impulse effect, huge damage can be not only caused to body, also nervous system can be caused not to a certain extent
Reversible damage.The H of high concentration2S gas in the olfactory nerves of the moment of contact paralysis human body can people can not perceive certainly
Oneself has been in danger.Moreover, H2S can also attack carbon steel and Kufil used in electronics industry, and in metal
Surface forms corrosion product or dendritic crystal palpus, and then forms sulfide film, enhances corrosivity.Due to H2S's is tight
It endangers again, how quickly to detect H2The presence of S gas is just particularly important.
It is the gas sensor of core due to low with manufacturing cost using metal oxide semiconductor material, synthesis technology letter
The advantages that single, was widely studied in recent years, mainly included tungsten oxide, titanium dioxide, zinc oxide, tin oxide and iron oxide etc.
Deng.Although these materials are to H2S gas has good sensitivity, preparation process also comparative maturity, but they have one altogether
Same disadvantage-response speed is not fast enough, i.e. the response time and recovery time is longer, substantially all in 10s or more.Shen Qing Publication
Number to disclose a kind of TiO of Co doping in the Chinese invention patent application of CN106645309A2The H of nano-pipe array thin film2S
Gas sensor, although the H2The recovery time of S gas sensor is in 3s or so, but the response time can only achieve at the soonest
7s.Due to H2S gas can cause greatly to injure to human body in a short time, therefore the response time of gas sensitive is shorter,
Value can be more shown in practical applications.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Li-La-Ti oxygen material, Li-La-Ti oxygen material obtained as
H2S gas sensitive is to H2S gas has the shorter response time.
The present invention also provides a kind of couple of H2S gas has the Li-La-Ti oxygen material and a kind of couple of H compared with short response time2S
Gas has the H compared with short response time2S gas sensor.
In order to achieve the goal above, technical solution used by the preparation method of Li-La-Ti oxygen material of the invention is:
A kind of preparation method of Li-La-Ti oxygen material, comprising the following steps:
1) lithium source, lanthanum source, complexing agent, titanium source, ethylene glycol, polyethylene glycol oxide and 1,2 epoxy prapane are provided and is dissolved in solvent shape
At solvent heat precursor liquid；
2) the solvent heat precursor liquid is warming up to 100~300 DEG C of 3~168h of reaction, is separated by solid-liquid separation, obtains Li-La-Ti
Oxygen presoma powder；
3) by resulting Li-La-Ti oxygen presoma powder be sintered to get.
Complexing agent-ethylene glycol complex system is introduced solvent-thermal method by the preparation method of Li-La-Ti oxygen material of the invention
In preparation process, complexing agent-ethylene glycol can form stable chelate with lithium, lanthanum, titanium ion, to make the energy of system most
Lowization, during subsequent solvent heat, chelate can tend to the spherical forming core of minimum energy, improve the ratio of Li-La-Ti oxygen material
Surface area.Meanwhile polyethylene glycol oxide and 1, the addition of 2- propylene oxide can effectively improve interface state, wherein polyoxygenated
Ethylene is the very extensive high-molecular compound of purposes, can be used as thickener, flocculant, lubricant, dispersing agent and surface-active
Agent etc., in the present invention, the addition of polyethylene glycol oxide reduce system inner surface tension, improve the stability of system, thus raw
At stable precursor solution, and porous structure is left after sintering, further increase the specific surface area of Li-La-Ti oxygen material, and
Hydrogen sulfide gas diffusion admittance is increased, is improved to H2The response sensitivity of S.Li-La-Ti oxygen material of the invention states preparation
Method and process process is simple, at low cost, yield is big, purity is high and repeatability are good, while carrying out tissue shape with can be convenient
Looks regulation, is very suitable to be mass produced, has good actual application prospect.
It is more uniform in order to mix solution, it is preferred that in step 1), the solvent heat precursor liquid is in lithium source, lanthanum
Source, complexing agent and titanium source are dissolved in addition polyethylene glycol oxide in the mixed solution of solvent formation and are dissolved, complete to polyethylene glycol oxide
Ethylene glycol is added after fully dissolved to mix, then adds the mixing of 1,2- propylene oxide.
Preferably, the average molecular mass of the polyethylene glycol oxide is 4 × 106~6 × 106.The polyoxy of macromolecule
Change the active effect of ethylene more preferably.
Preferably, in order to keep mixed solution system more stable, titanium atom and 1 in the titanium source, 2- propylene oxide
Molar ratio be 1:0.2~0.8；The mass ratio of polyethylene glycol oxide and 1,2 epoxy prapane is 1:0.57~3.16.
Preferably, the complexing agent is citric acid；In order to keep chelating agent mixing more uniform, titanium atom, complexing in titanium source
The molar ratio of agent and ethylene glycol is 1:2~5:1~10.
Technical solution used by Li-La-Ti oxygen material of the invention are as follows:
Li-La-Ti oxygen material made from a kind of preparation method using above-mentioned Li-La-Ti oxygen material.
Li-La-Ti oxygen material of the invention, since material itself belongs to typical n-type semiconductor perovskite material, certain
At a temperature of, it can be chemically reacted with hydrogen sulfide, so as to cause resistance variations, and the pattern that the method is made is porous knot
Structure accelerates the transmission of hydrogen sulfide gas, can be to H2When S gas shows the response speed being exceedingly fast, response time and recovery
Between it is average all within 3s, most can reach 1s fastly, and to H2S gas has highly sensitive and excellent selectivity.
H of the invention2The scheme of technology used by S gas sensor are as follows:
A kind of H using above-mentioned Li-La-Ti oxygen material2S gas sensor.
H of the invention2S gas sensor, using Li-La-Ti oxygen material of the invention as H2S gas sensitive, using routine
The preparation method of gas sensor is made.H of the invention2S gas sensor is to H2S gas has excellent sensitivity and selection
Property.
Detailed description of the invention
Fig. 1 is the X-ray of Li-La-Ti oxygen material made from the embodiment 1 of the preparation method of Li-La-Ti oxygen material of the invention
Diffraction pattern；
Fig. 2 is Li-La-Ti oxygen scanning of materials electricity made from the embodiment 1 of the preparation method of Li-La-Ti oxygen material of the invention
Mirror figure；
Fig. 3 is Li-La-Ti oxygen material made from the embodiment 1 of the preparation method of Li-La-Ti oxygen material of the invention in difference
At a temperature of to 5-50ppm H2The response sensitivity of S gas；
Fig. 4 be in the embodiment 1 of the preparation method of Li-La-Ti oxygen material of the invention Li-La-Ti oxygen material obtained 340
To 5-50ppm H at DEG C2The voltage response curves of S gas；
Fig. 5 is Li-La-Ti oxygen material made from the embodiment 1 of the preparation method of Li-La-Ti oxygen material of the invention at 340 DEG C
Under to the response sensitivity of 50ppm gas with various；
Fig. 6 is Li-La-Ti oxygen material made from the embodiment 2 of the preparation method of Li-La-Ti oxygen material of the invention at 340 DEG C
Under to 50ppm H2The voltage response curves of S gas；
Fig. 7 is that Li-La-Ti oxygen material made from the Examples 1 to 5 of the preparation method of Li-La-Ti oxygen material of the invention exists
To 50ppm H at 340 DEG C2The response time and recovery time of S gas.
Specific embodiment
The preparation method of Li-La-Ti oxygen material provided by the invention, comprising the following steps:
1) lithium source, lanthanum source, complexing agent, titanium source, ethylene glycol, polyethylene glycol oxide and 1,2 epoxy prapane are provided and is dissolved in solvent shape
At solvent heat precursor liquid；
2) the solvent heat precursor liquid is warming up to 100~300 DEG C of 3~168h of reaction, is separated by solid-liquid separation, obtains Li-La-Ti
Oxygen presoma powder；
3) by resulting Li-La-Ti oxygen presoma powder be sintered to get.
Li-La-Ti oxygen material of the invention is perovskite structure, chemical general formula Li3xLa2/3-xTiO3, 0 < x < 2/3 in formula.
Elemental lithium in lithium source in solvent heat precursor liquid, the molar ratio of titanium atom is 3x:(2/3-x in lanthanum element and titanium source in lanthanum source): 1,
Wherein 0 < x < 2/3.
Preferably, in step 1), the solvent heat precursor liquid is to be dissolved in solvent shape in lithium source, lanthanum source, complexing agent and titanium source
At mixed solution in be added polyethylene glycol oxide dissolved, after polyethylene glycol oxide is completely dissolved be added ethylene glycol mix, so
After add 1,2 epoxy prapane mixing.It is dissolved to accelerate polyethylene glycol oxide in mixed solution, it can be in polyethylene glycol oxide
System is heated afterwards.
Preferably, the mixed solution is to add titanium source after lithium source, lanthanum source and complexing agent are dissolved in solvent and be uniformly mixed
It obtains.The titanium source can use titanate esters, preferably butyl titanate.The lithium source selection dissolves in the lithium of used solvent
Source, such as lithium nitrate.The lanthanum source selection dissolves in the lanthanum source of used solvent, such as can choose lanthanum nitrate.
Preferably, the solvent that the solvent heat precursor liquid uses is ethyl alcohol.Mole of titanium atom and ethyl alcohol in the titanium source
Than for 1:120~170.
Preferably, the relative molecular mass of the polyethylene glycol oxide is 5 × 106。
Preferably, titanium atom and 1 in the titanium source, the molar ratio of 2- propylene oxide are 1:0.2~0.8.Further preferably
, titanium atom and 1 in the titanium source, the molar ratio of 2- propylene oxide is 1:0.5~0.65.Preferably, polyethylene glycol oxide and 1,
The mass ratio of 2- propylene oxide is 1:0.57~3.16.
Preferably, the complexing agent is citric acid.The citric acid formed when using citric acid as complexing agent-ethylene glycol complexing
Body can further decrease the energy of system, and during subsequent solvent heat, chelate can tend to the spherical shape of minimum energy
Core improves the specific surface area of Li-La-Ti oxygen material.In titanium source the molar ratio of titanium atom, complexing agent and ethylene glycol be 1:2~5:1~
10。
Preferably, the molar ratio of titanium atom, complexing agent and ethylene glycol is 1:3~5:1~10 in titanium source.
Preferably, the molar ratio of titanium atom, complexing agent and ethylene glycol is 1:2~5:6~10 in titanium source.
Preferably, in step 2), the reaction closed progress in the reactor.Preferably, the reactor is that high temperature is high
Press reaction kettle.Compactedness of the solvent heat precursor liquid in the reactor is no more than the 3/4 of the reactor volume, preferably
The 2/3~3/4 of the reactor volume.
Preferably, in step 2), time of the reaction is 5~for 24 hours.
Preferably, the temperature of the sintering is 600~1000 DEG C.The time of the sintering is 1~12h.
Preferably, the rate that sintering temperature is warming up to before sintering is 3~5 DEG C/min.
Separation of solid and liquid in step 2) is centrifugation or filtering.
In order to improve the purity of Li-La-Ti oxygen precursor powder, it is preferred that step 2) further include will be separated by solid-liquid separation it is resulting solid
Body is washed.Preferably, by be separated by solid-liquid separation resulting solid carry out washing use detergent with solvent heat in step 1) before
Drive the solvent that liquid uses.Preferably, step 2) further includes that by the solid after being separated by solid-liquid separation or will be separated by solid-liquid separation resulting solid
It is ground again after being washed, presoma nano-powder is obtained after grinding.Preferably, resulting solid to being separated by solid-liquid separation before grinding
Body is dried.The temperature of the drying process is 60~80 DEG C.
H provided by the invention2S gas sensor is metal oxide semiconductor sensor.
It is further described below in conjunction with specific embodiment technical solution of the present invention.
Since during preparing Li-La-Ti oxygen material, especially during the sintering process, Li is possible to that others can be participated in
Side reaction generates Li2CO3, LiOH, and will cause Li volatilization, use in the preparation method of the Li-La-Ti oxygen material of each embodiment
Lithium source is excessive.
The embodiment 1 of the preparation method of Li-La-Ti oxygen material
Li-La-Ti oxygen (the Li of the present embodiment0.5La0.5TiO3) material preparation method, comprising the following steps:
1) successively by 0.005mol lanthanum nitrate (La (NO3)3·6H2O), 0.0055mol lithium nitrate (LiNO3), 0.03mol
Citric acid monohydrate closes object, is added in 1.65mol dehydrated alcohol, stirs to mixture after being completely dissolved, be slowly added at room temperature
0.01mol butyl titanate, after being stirred 20min, 0.12g polyethylene glycol oxide is added, and (relative molecular mass is 5 × 106) simultaneously
Heated solution is until polyethylene glycol oxide is completely dissolved, and then to 0.1mol ethylene glycol is slowly added dropwise in solution, stirs after 20min again
0.005mol 1 is slowly added dropwise, 2- propylene oxide stirs 40min, obtains uniform solvent heat precursor liquid；
2) in the stainless steel cauldron for the polytetrafluoroethyllining lining that the resulting solvent heat precursor liquid of step 1) is fitted into 100mL
(compactedness is the 3/4 of reactor volume), is warming up to 180 DEG C, reacts 6h, take out reaction kettle after complete reaction after sealing, from
It is so cooled to room temperature, centrifugation obtains composite granule；
3) by the resulting composite granule of step 2) with dehydrated alcohol be centrifuged 3 times, centrifugal speed 8000r/min, every time from
The heart time is 4min, then in 80 DEG C of dry 8h, then in agate mortar grinding is uniform, obtain Li-La-Ti oxygen presoma powder；
4) Li-La-Ti oxygen presoma powder obtained in step 3) is taken, with the heating rate of 5 DEG C/min, is sintered at 700 DEG C
3h obtains H2The Li-La-Ti oxygen nano material of S sensitivity to get.
Li-La-Ti oxygen nano material made from preparation method by the present embodiment carries out XRD test and SEM test.XRD is surveyed
It tries resulting X-ray diffractogram and sees Fig. 1, it can be seen from the figure that exactly matching with standard card 89-4928, illustrate preparation
Li-La-Ti oxygen nano material crystallization purity is high.SEM tests resulting scanning electron microscope (SEM) photograph and sees Fig. 2, it can be seen from the figure that being prepared into
The Li-La-Ti oxygen nano material microstructure arrived is in porous spherical, and good dispersion, each section ingredient is uniform, partial size 300~
550nm。
The embodiment 2 of the preparation method of Li-La-Ti oxygen material
Li-La-Ti oxygen (the Li of the present embodiment0.5La0.5TiO3) material preparation method, comprising the following steps:
1) successively by 0.005mol lanthanum nitrate (La (NO3)3·6H2O), 0.0055mol lithium nitrate (LiNO3), 0.03mol
Citric acid is added in 1.65mol dehydrated alcohol, stirs at room temperature to mixture after being completely dissolved, is slowly added to 0.01mol metatitanic acid
Four butyl esters, after being stirred 20min, 0.12g polyethylene glycol oxide is added, and (relative molecular mass is 5 × 106) and heated solution it is straight
It is completely dissolved to polyethylene glycol oxide, then to 0.09mol ethylene glycol is slowly added dropwise in solution, is slowly added dropwise again after stirring 20min
0.005mol 1,2- propylene oxide stir 40min, obtain uniform solvent heat precursor liquid；
2) in the stainless steel cauldron for the polytetrafluoroethyllining lining that the resulting solvent heat precursor liquid of step 1) is fitted into 100mL
(compactedness is the 3/4 of reactor volume), is warming up to 150 DEG C, reacts 6h, take out reaction kettle after complete reaction after sealing, from
It is so cooled to room temperature, composite granule is obtained by filtration；
3) by the resulting composite granule of step 2) with dehydrated alcohol be centrifuged 3 times, centrifugal speed 8000r/min, every time from
The heart time is 4min, then in 80 DEG C of dry 8h, then in agate mortar grinding is uniform, obtain Li-La-Ti oxygen presoma powder；
4) Li-La-Ti oxygen presoma powder obtained in step 3) is taken, with the heating rate of 5 DEG C/min, is sintered at 700 DEG C
3h obtains H2The Li-La-Ti oxygen nano material of S sensitivity to get.
The embodiment 3 of the preparation method of Li-La-Ti oxygen material
Li-La-Ti oxygen (the Li of the present embodiment0.5La0.5TiO3) material preparation method, comprising the following steps:
1) successively by 0.005mol lanthanum nitrate (La (NO3)3·6H2O), 0.0055mol lithium nitrate (LiNO3), 0.03mol
Citric acid is added in 1.38mol dehydrated alcohol, stirs at room temperature to mixture after being completely dissolved, is slowly added to 0.01mol metatitanic acid
Four butyl esters, after being stirred 20min, 0.12g polyethylene glycol oxide is added, and (relative molecular mass is 5 × 106) and heated solution it is straight
It is completely dissolved to polyethylene glycol oxide, then to 0.06mol ethylene glycol is slowly added dropwise in solution, is slowly added dropwise again after stirring 20min
0.005mol 1,2- propylene oxide stir 40min, obtain uniform solvent heat precursor liquid；
2) in the stainless steel cauldron for the polytetrafluoroethyllining lining that the resulting solvent heat precursor liquid of step 1) is fitted into 100mL
(compactedness is the 3/4 of reactor volume), is warming up to 140 DEG C, reacts 5h, take out reaction kettle after complete reaction after sealing, from
It is so cooled to room temperature, composite granule is obtained by filtration；
3) by the resulting composite granule of step 2) with dehydrated alcohol be centrifuged 3 times, centrifugal speed 8000r/min, every time from
The heart time is 4min, then in 80 DEG C of dry 8h, then in agate mortar grinding is uniform, obtain Li-La-Ti oxygen presoma powder；
4) Li-La-Ti oxygen presoma powder obtained in step 3) is taken, with the heating rate of 4 DEG C/min, is sintered at 700 DEG C
3h obtains H2The Li-La-Ti oxygen nano material of S sensitivity to get.
The embodiment 4 of the preparation method of Li-La-Ti oxygen material
Li-La-Ti oxygen (the Li of the present embodiment0.5La0.5TiO3) material preparation method, comprising the following steps:
1) successively by 0.005mol lanthanum nitrate (La (NO3)3·6H2O), 0.0055mol lithium nitrate (LiNO3), 0.03mol
Citric acid is added in 1.38mol dehydrated alcohol, stirs at room temperature to mixture after being completely dissolved, is slowly added to 0.01mol metatitanic acid
Four butyl esters, after being stirred 20min, 0.5g polyethylene glycol oxide is added, and (relative molecular mass is 5 × 106) and heated solution until
Polyethylene glycol oxide is completely dissolved, and then to 0.06mol ethylene glycol is slowly added dropwise in solution, is slowly added dropwise again after stirring 20min
0.005mol 1,2- propylene oxide stir 40min, obtain uniform solvent heat precursor liquid；
2) in the stainless steel cauldron for the polytetrafluoroethyllining lining that the resulting solvent heat precursor liquid of step 1) is fitted into 100mL
(compactedness is the 3/4 of reactor volume), is warming up to 180 DEG C, reacts 5h, take out reaction kettle after complete reaction after sealing, from
It is so cooled to room temperature, composite granule is obtained by filtration；
3) by the resulting composite granule of step 2) with dehydrated alcohol be centrifuged 3 times, centrifugal speed 8000r/min, every time from
The heart time is 4min, then in 80 DEG C of dry 8h, then in agate mortar grinding is uniform, obtain Li-La-Ti oxygen presoma powder；
4) Li-La-Ti oxygen presoma powder obtained in step 3) is taken, with the heating rate of 3 DEG C/min, is sintered at 700 DEG C
3h obtains H2The Li-La-Ti oxygen nano material of S sensitivity to get.
The embodiment 5 of the preparation method of Li-La-Ti oxygen material
Li-La-Ti oxygen (the Li of the present embodiment0.5La0.5TiO3) material preparation method, comprising the following steps:
1) successively by 0.005mol lanthanum nitrate (La (NO3)3·6H2O), 0.0055mol lithium nitrate (LiNO3), 0.03mol
Citric acid is added in 1.24mol dehydrated alcohol, stirs at room temperature to mixture after being completely dissolved, is slowly added to 0.01mol metatitanic acid
Four butyl esters, after being stirred 20min, 0.12g polyethylene glycol oxide is added, and (relative molecular mass is 5 × 106) and heated solution it is straight
It is completely dissolved to polyethylene glycol oxide, then to 0.06mol ethylene glycol is slowly added dropwise in solution, is slowly added dropwise again after stirring 20min
0.005mol 1,2- propylene oxide stir 40min, obtain uniform solvent heat precursor liquid；
2) in the stainless steel cauldron for the polytetrafluoroethyllining lining that the resulting solvent heat precursor liquid of step 1) is fitted into 100mL
(compactedness is the 3/4 of reactor volume), is warming up to 180 DEG C, reacts 6h, take out reaction kettle after complete reaction after sealing, from
It is so cooled to room temperature, composite granule is obtained by filtration；
3) by the resulting composite granule of step 2) with dehydrated alcohol be centrifuged 3 times, centrifugal speed 8000r/min, every time from
The heart time is 4min, then in 80 DEG C of dry 8h, then in agate mortar grinding is uniform, obtain Li-La-Ti oxygen presoma powder；
4) Li-La-Ti oxygen presoma powder obtained in step 3) is taken, with the heating rate of 5 DEG C/min, is sintered at 650 DEG C
3h obtains H2The Li-La-Ti oxygen nano material of S sensitivity to get.
The embodiment 6 of the preparation method of Li-La-Ti oxygen material
Li-La-Ti oxygen (the Li of the present embodiment0.5La0.5TiO3) material preparation method, comprising the following steps:
1) successively by 0.005mol lanthanum nitrate (La (NO3)3·6H2O), 0.0055mol lithium nitrate (LiNO3), 0.045mol
Citric acid is added in 1.51mol dehydrated alcohol, stirs at room temperature to mixture after being completely dissolved, is slowly added to 0.01mol metatitanic acid
Four butyl esters, after being stirred 20min, 0.12g polyethylene glycol oxide is added, and (relative molecular mass is 5 × 106) and heated solution it is straight
It is completely dissolved to polyethylene glycol oxide, then to 0.06mol ethylene glycol is slowly added dropwise in solution, is slowly added dropwise again after stirring 20min
0.006mol 1,2- propylene oxide stir 40min, obtain uniform solvent heat precursor liquid；
2) in the stainless steel cauldron for the polytetrafluoroethyllining lining that the resulting solvent heat precursor liquid of step 1) is fitted into 100mL
(compactedness is the 3/4 of reactor volume), is warming up to 100 DEG C, reacts 18h, take out reaction kettle after complete reaction after sealing, from
It is so cooled to room temperature, composite granule is obtained by filtration；
3) by the resulting composite granule of step 2) with dehydrated alcohol be centrifuged 3 times, centrifugal speed 8000r/min, every time from
The heart time is 4min, then in 80 DEG C of dry 8h, then in agate mortar grinding is uniform, obtain Li-La-Ti oxygen presoma powder；
4) Li-La-Ti oxygen presoma powder obtained in step 3) is taken, with the heating rate of 5 DEG C/min, is sintered at 1000 DEG C
3h obtains H2The Li-La-Ti oxygen nano material of S sensitivity to get.
The embodiment 7 of the preparation method of Li-La-Ti oxygen material
Li-La-Ti oxygen (the Li of the present embodiment0.5La0.5TiO3) material preparation method, comprising the following steps:
1) successively by 0.005mol lanthanum nitrate (La (NO3)3·6H2O), 0.0055mol lithium nitrate (LiNO3), 0.05mol
Citric acid is added in 1.65mol dehydrated alcohol, stirs at room temperature to mixture after being completely dissolved, is slowly added to 0.01mol metatitanic acid
Four butyl esters, after being stirred 20min, 0.12g polyethylene glycol oxide is added, and (relative molecular mass is 5 × 106) and heated solution it is straight
It is completely dissolved to polyethylene glycol oxide, then to 0.1mol ethylene glycol is slowly added dropwise in solution, is slowly added dropwise again after stirring 20min
0.0065mol 1,2- propylene oxide stir 40min, obtain uniform solvent heat precursor liquid；
2) in the stainless steel cauldron for the polytetrafluoroethyllining lining that the resulting solvent heat precursor liquid of step 1) is fitted into 100mL
(compactedness is the 3/4 of reactor volume), is warming up to 300 DEG C after sealing, reaction for 24 hours, takes out reaction kettle after complete reaction, from
It is so cooled to room temperature, composite granule is obtained by filtration；
3) by the resulting composite granule of step 2) with dehydrated alcohol be centrifuged 3 times, centrifugal speed 8000r/min, every time from
The heart time is 4min, then in 80 DEG C of dry 8h, then in agate mortar grinding is uniform, obtain Li-La-Ti oxygen presoma powder；
4) Li-La-Ti oxygen presoma powder obtained in step 3) is taken, with the heating rate of 5 DEG C/min, is sintered at 800 DEG C
3h obtains H2The Li-La-Ti oxygen nano material of S sensitivity to get.
The embodiment 8 of the preparation method of Li-La-Ti oxygen material
Li-La-Ti oxygen (the Li of the present embodiment0.5La0.5TiO3) material preparation method, comprising the following steps:
1) successively by 0.005mol lanthanum nitrate (La (NO3)3·6H2O), 0.0055mol lithium nitrate (LiNO3), 0.02mol
Citric acid is added in 1.7mol dehydrated alcohol, stirs at room temperature to mixture after being completely dissolved, is slowly added to 0.01mol metatitanic acid four
Butyl ester, after being stirred 20min, 0.04g polyethylene glycol oxide is added, and (relative molecular mass is 5 × 106) and heated solution until
Polyethylene glycol oxide is completely dissolved, and then to 0.1mol ethylene glycol is slowly added dropwise in solution, is slowly added dropwise again after stirring 20min
0.002mol 1,2- propylene oxide stir 40min, obtain uniform solvent heat precursor liquid；
2) in the stainless steel cauldron for the polytetrafluoroethyllining lining that the resulting solvent heat precursor liquid of step 1) is fitted into 100mL
(compactedness is the 3/4 of reactor volume), is warming up to 300 DEG C, reacts 3h, take out reaction kettle after complete reaction after sealing, from
It is so cooled to room temperature, composite granule is obtained by filtration；
3) by the resulting composite granule of step 2) with dehydrated alcohol be centrifuged 3 times, centrifugal speed 8000r/min, every time from
The heart time is 4min, then in 80 DEG C of dry 8h, then in agate mortar grinding is uniform, obtain Li-La-Ti oxygen presoma powder；
4) Li-La-Ti oxygen presoma powder obtained in step 3) is taken, with the heating rate of 5 DEG C/min, is sintered at 1000 DEG C
1h obtains H2The Li-La-Ti oxygen nano material of S sensitivity to get.
The embodiment 9 of the preparation method of Li-La-Ti oxygen material
Li-La-Ti oxygen (the Li of the present embodiment0.5La0.5TiO3) material preparation method, comprising the following steps:
1) successively by 0.005mol lanthanum nitrate (La (NO3)3·6H2O), 0.0055mol lithium nitrate (LiNO3), 0.05mol
Citric acid is added in 1.2mol dehydrated alcohol, stirs at room temperature to mixture after being completely dissolved, is slowly added to 0.01mol metatitanic acid four
Butyl ester, after being stirred 20min, 0.28g polyethylene glycol oxide is added, and (relative molecular mass is 5 × 106) and heated solution it is straight
It is completely dissolved to polyethylene glycol oxide, then to 0.1mol ethylene glycol is slowly added dropwise in solution, is slowly added dropwise again after stirring 20min
0.008mol 1,2- propylene oxide stir 40min, obtain uniform solvent heat precursor liquid；
2) in the stainless steel cauldron for the polytetrafluoroethyllining lining that the resulting solvent heat precursor liquid of step 1) is fitted into 100mL
(compactedness is the 3/4 of reactor volume), is warming up to 100 DEG C, reacts 168h, take out reaction kettle after complete reaction after sealing,
Composite granule is obtained by filtration in cooled to room temperature；
3) by the resulting composite granule of step 2) with dehydrated alcohol be centrifuged 3 times, centrifugal speed 8000r/min, every time from
The heart time is 4min, then in 80 DEG C of dry 8h, then in agate mortar grinding is uniform, obtain Li-La-Ti oxygen presoma powder；
4) Li-La-Ti oxygen presoma powder obtained in step 3) is taken, with the heating rate of 5 DEG C/min, is sintered at 600 DEG C
12h obtains H2The Li-La-Ti oxygen nano material of S sensitivity to get.
The embodiment of Li-La-Ti oxygen material
The Li-La-Ti oxygen material of the present embodiment is made by the Examples 1 to 9 of the preparation method of Li-La-Ti oxygen material respectively, this
Place repeats no more.
H2The embodiment 1 of S gas sensor
The H of the present embodiment2S gas sensor is with lithium lanthanum made from the embodiment 1 of the preparation method of lithium lanthanum oxygen titanium material
Titanyl material is as H2The heater-type gas sensor of S gas sensitive is a kind of metal oxide semiconductor sensor.
The H of the present embodiment2The preparation method of S gas sensor, comprising the following steps:
The H of the present embodiment is tested using WS-30A type Testing system of gas-sensor built2S gas sensor is right at different temperatures
5-50ppm H2The response sensitivity of S gas, test result are shown in Fig. 3, from figure 3, it can be seen that the preparation of Li-La-Ti oxygen material
The optimum working temperature of Li-La-Ti oxygen material prepared by the embodiment 1 of method is 340 DEG C, and highest response sensitivity is up to 4.25.
The H of the present embodiment is tested using WS-30A type Testing system of gas-sensor built2S gas sensor at 340 DEG C to 5~
50ppm H2The response voltage of S gas, obtains voltage response curves as shown in Figure 4.Figure 4, it is seen that Li-La-Ti oxygen
Li-La-Ti oxygen material prepared by the embodiment 1 of the preparation method of material is to H2S air-sensitive response performance is sufficiently stable, in different H2S is dense
Also the response speed being exceedingly fast is able to maintain under degree.
The H of the present embodiment is tested using WS-30A type Testing system of gas-sensor built2S gas sensor is right at 340 DEG C
The response sensitivity of 50ppm gas with various, test results are shown in figure 5.From figure 5 it can be seen that the system of Li-La-Ti oxygen material
Li-La-Ti oxygen material prepared by the embodiment 1 of Preparation Method is to H2The sensitivity of other gases other than S is extremely low, is almost not responding to,
To H2S gas-selectively is splendid.
H2The embodiment 2~9 of S gas sensor
H2H in the embodiment 2~9 of S gas sensor2S gas sensor and H2H in the embodiment 1 of S gas sensor2S
The difference of gas sensor is only that: H2The H used in the embodiment 2~9 of S gas sensor2S gas sensitive is followed successively by lithium lanthanum
The Li-La-Ti oxygen material being prepared in the embodiment 2~9 of the preparation method of titanyl material does not address the completely same H of content2S gas
The embodiment 1 of dependent sensor.
Experimental example 1
H is tested using WS-30A type Testing system of gas-sensor built2The H of the embodiment 2 of S gas sensor2S gas sensor
To 50ppm H at 340 DEG C2The response voltage of S gas draws voltage response curves, sees Fig. 6.From fig. 6 it can be seen that lithium
Li-La-Ti oxygen material prepared by the embodiment 2 of the preparation method of lanthanum titanyl material is to H2S gas has the response speed being exceedingly fast, and rings
Between seasonable and recovery time all only has 1s.
Experimental example 2
H is tested using WS-30A type Testing system of gas-sensor built2The H of the Examples 1 to 5 of S gas sensor2S gas sensing
Device is at 340 DEG C to 50ppm H2The response time and recovery time of S gas, as a result see Fig. 7.It can be seen from figure 7 that lithium lanthanum
Prepared Li-La-Ti oxygen material is to H in the embodiment 1-5 of the preparation method of titanyl2The response-recovery time of S gas is in 1-
Between 3s, illustrate that Li-La-Ti oxygen material obtained by the preparation method using Li-La-Ti oxygen material of the invention can be to H2S gas
Body is exceedingly fast response.
Claims (7)
1. a kind of preparation method of Li-La-Ti oxygen material, it is characterised in that: the following steps are included:
1) lithium source, lanthanum source, complexing agent, titanium source, ethylene glycol, polyethylene glycol oxide and 1,2 epoxy prapane are provided and are dissolved in solvent formation
Solvent heat precursor liquid；
2) the solvent heat precursor liquid is warming up to 100~300 DEG C of 3~168h of reaction, be separated by solid-liquid separation, before obtaining Li-La-Ti oxygen
Drive body powder；
3) by resulting Li-La-Ti oxygen presoma powder be sintered to get.
2. the preparation method of Li-La-Ti oxygen material according to claim 1, it is characterised in that: in step 1), the solvent
Hot precursor liquid is that polyethylene glycol oxide is added in the mixed solution that lithium source, lanthanum source, complexing agent and titanium source are dissolved in solvent formation to carry out
Dissolution is added ethylene glycol after polyethylene glycol oxide is completely dissolved and mixes, and then adds the mixing of 1,2- propylene oxide.
3. the preparation method of Li-La-Ti oxygen material according to claim 1 or 2, it is characterised in that: the polyethylene glycol oxide
Relative molecular mass be 4 × 106~6 × 106。
4. the preparation method of Li-La-Ti oxygen material according to claim 3, it is characterised in that: in the titanium source titanium atom and
The molar ratio of 1,2 epoxy prapane is 1:0.2~0.8；The mass ratio of polyethylene glycol oxide and 1,2 epoxy prapane be 1:0.57~
3.16。
5. the preparation method of Li-La-Ti oxygen material according to claim 1 or 2, it is characterised in that: the complexing agent is lemon
Lemon acid；The molar ratio of titanium atom, complexing agent and ethylene glycol is 1:2~5:1~10 in titanium source.
6. Li-La-Ti oxygen material made from a kind of preparation method using Li-La-Ti oxygen material as described in claim 1.
7. a kind of H using Li-La-Ti oxygen material as claimed in claim 62S gas sensor.
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| CN113277551A (en) * | 2021-05-19 | 2021-08-20 | 郑州大学 | Composite lithium lanthanum titanate material, preparation method and application |
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